Deuterium NMR is used to investigate the phase behavior of membranes containing ergosterol and to measure the temperature-ergosterol mole fraction phase diagram. In particular, our approach to analyzing the NMR spectra has allowed us to definitively locate and characterize the region where two liquid crystalline phases coexist. The general methodology for phase boundary determination in phospholipid/sterol membranes is presented. (c) 2005 Wiley Periodicals, Inc.